Determination of urinary phytoestrogens by HPLC-MS/MS: A comparison of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI).

Determination of urinary phytoestrogens by HPLC-MS/MS: A comparison of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). Research Abstract Details 

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Determination of urinary phytoestrogens by HPLC-MS/MS: A comparison of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). Abstract Text:

Michael E Rybak,Daniel L Parker,Christine M Pfeiffer,

A comparison of the analytical performance of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) for the quantitative determination of six urinary phytoestrogens (daidzein, O-desmethylangolensin, equol, enterodiol, enterolactone and genistein) by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) is presented here. Both APCI and ESI were suitable for the analysis of these compounds; however, ESI did improve measurement imprecision and sensitivity in certain cases. Method imprecision (between-run coefficients of variation [CVs] from duplicate analysis of three quality control [QC] urine pools across 20 runs) was 5.6-12% for ESI, as opposed to 5.3-30% for APCI. At low concentrations (3-60ng/mL, analyte dependent) imprecision was lower with ESI, whereas both techniques were generally commensurate at high concentrations (200-1000ng/mL, analyte dependent). Method accuracy (spiked analyte recovery from the QC pools) was comparable between techniques: 86-114% for ESI; 95-105% for APCI. Limits of detection (LODs) were equivalent or better with ESI compared to APCI, with the most significant LOD improvement observed for equol (ESI: 0.3ng/mL; APCI: 2.7ng/mL). This translated into a substantial increase in equol detection frequency (% of sample results above LOD) within a random patient sample subset (98% for ESI, compared to 81% for APCI, n=378). Correlation (Pearson) and agreement (Deming regression, Bland-Altman bias) between ESI and APCI results in the patient subset was better in cases where imprecision and sensitivity was similar for both techniques (daidzein, enterolactone, genistein: r=0.993-0.998; slope=0.98-1.03; bias=-4.2 to -0.8%); correlation and/or agreement was poorer for analytes, where APCI imprecision and sensitivity were inferior (equol, O-desmethylangolensin, enterodiol). Baring significant factors arising from differences in ionization source design, these observations suggest that ESI is more appropriate for urinary biomonitoring of these compounds by LC-MS/MS.

Determination of urinary phytoestrogens by HPLC-MS/MS: A comparison of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). Publishing Authors By Initials

ME Rybak,DL Parker,CM Pfeiffer,

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Determination of urinary phytoestrogens by HPLC-MS/MS: A comparison of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of chromatography. B, Analytical technolog

VOLUME: 861

Page Numbers: 145-50

Journal Abbreviation: J. Chromatogr. B Analyt. Techn

ISSN: 1570-0232

DAY: 21

MONTH: 11

YEAR: 2007

Determination of urinary phytoestrogens by HPLC-MS/MS: A comparison of atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI). Information

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LANGUAGE: eng

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AFFILIATION: Centers for Disease Control and Prevention, National Center for Environmental Health, Atlanta, GA 30341, USA.

Country: Netherlands

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MEDLINETA: J Chromatogr B Analyt Technol

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